EP0095199B1 - Reactor for preparing chlorine dioxide - Google Patents
Reactor for preparing chlorine dioxide Download PDFInfo
- Publication number
- EP0095199B1 EP0095199B1 EP83200595A EP83200595A EP0095199B1 EP 0095199 B1 EP0095199 B1 EP 0095199B1 EP 83200595 A EP83200595 A EP 83200595A EP 83200595 A EP83200595 A EP 83200595A EP 0095199 B1 EP0095199 B1 EP 0095199B1
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- European Patent Office
- Prior art keywords
- gas
- immersed
- reactor
- reaction
- conical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
- B01D3/18—Fractionating columns in which vapour bubbles through liquid with horizontal bubble plates
- B01D3/20—Bubble caps; Risers for vapour; Discharge pipes for liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
- B01D3/24—Fractionating columns in which vapour bubbles through liquid with sloping plates or elements mounted stepwise
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/025—Preparation from chlorites or chlorates from chlorates without any other reaction reducing agent than chloride ions
Definitions
- the invention relates to a reactor for the production of chlorine dioxide.
- Chlorine dioxide is increasingly being obtained through the action of hydrochloric acid on sodium chlorate. Since chlorine dioxide is extremely explosive at higher temperatures, the process is carried out at a relatively low temperature and with overflow vessels one behind the other or in a reaction column. Here you can through a series of cascaded and staggered in height reaction vessels, the z. B. are arranged as a column, chlorate and hydrochloric acid solutions flow through. In the opposite direction, one presses or sucks a stream of inert gas, e.g. B. air or nitrogen to rinse out the chlorine dioxide formed in the individual reaction rooms and thereby dilute to harmless concentrations. The gas flows through the liquid by means of gas line pipes or gas immersions reaching to the bottom of the reaction spaces.
- inert gas e.g. B. air or nitrogen
- the second reaction gives no chlorine dioxide. This reaction must therefore be suppressed as much as possible. A prerequisite for this is a minimal HCI excess in the reaction liquid. This in turn requires long dwell times, especially when the partially used electrolyte solution is recirculated to chlorate electrolysis, as in the so-called Kesting or Kunststoff process. In this case, residual hydrochloric acid would be decomposed to hydrogen and chlorine in the electrolysis. However, both are undesirable products in chlorate electrolysis. In order to avoid these undesired products, a ClO 2 reactor must be divided into several stages or reaction spaces, e.g. B. in six, as known from the Kesting process. In the top 4 reaction chambers, CI0 2 is generated at temperatures rising from top to bottom.
- the remaining hydrochloric acid is reacted with the NaCl0 3 still present to produce NaCl, CI 2 and H 2 0 by increasing the temperature to the boiling point.
- the Cl0 2 reactors are often made of titanium.
- the upper stages of a reactor run at low temperatures and could therefore be made of materials other than titanium, e.g. B. made of materials based on ceramic or plastic material.
- the CI0 2 To avoid decomposition of the chlorine dioxide, the CI0 2 must be reduced to a partial pressure of approx. 0.1 at. This is done by applying reduced pressure or by dilution with air or a combination of both.
- the design of the reactor must therefore be designed for vacuum and pressure.
- the air In order to strip the CI0 2 from the solution and not to stop the formation reaction of the chlorine dioxide (equation 1), the air must be bubbled through or sucked through the reaction solution.
- the resistance of the reaction liquid can now be used to build up a negative pressure, the vacuum advantageously increasing with increasing CI0 2 concentration.
- the object of the invention is to eliminate these disadvantages.
- the invention is based on a reactor for the production of chlorine dioxide from sodium chlorate and hydrochloric acid with the introduction of a carrier gas countercurrent, the reactor having a plurality of reaction spaces which are arranged vertically one above the other and are connected to one another by gas immersion or gas introduction and by submerged liquid overflows.
- the figure of the drawing shows a schematic representation of a longitudinal section through a reactor according to the invention.
- an aqueous solution of sodium chlorate and hydrogen chloride is introduced into the reactor 8 via line 1 and the used reaction solution is discharged via line 6.
- a carrier gas stream of inert gas is introduced in countercurrent via line 2.
- 3 denotes the bottom of the reaction chamber which rises in the shape of a cone, and 4 denotes the gas immersion 4 which is configured above the base 3 in the shape of a cone or funnel 4.
- the tubes 5 cause the reaction liquid to overflow from the respective reaction chamber located above it.
- V 1 and V 2 are practically the same liquid volume of the individual reaction chambers with the respective points of contact or lines S.
- the liquid column lying above the gas outlet point of the immersion 4 is designated FI.
- the volume of the reaction liquid inside the inlet ring (V 1) and outside the inlet ring (V 2) is practically the same and, consequently, the volumes also have practically the same weight.
- the point of exit of the gas flow from carrier gas such as air and reaction gas, such as chlorine dioxide and chlorine lies in the individual reaction chambers, so to speak, at the intersection S of the two volumes (see figure) and thus exactly below the respective liquid column (Fl). Since the pressure of the gas thus corresponds exactly to the weight of the liquid column above it and the gas is also sucked through, the reactor is relieved during operation.
- the advantage of the reactor according to the invention lies in the particularly favorable compact design with economically favorable, low sheet thicknesses of the reaction trays made of high-quality material such as titanium, as well as in short lines and small space requirements.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
- Static Random-Access Memory (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Die Erfindung betrifft einen Reaktor für die Herstellung von Chlordioxid.The invention relates to a reactor for the production of chlorine dioxide.
Chlordioxid wird in zunehmendem Masse durch Einwirkung von Chlorwasserstoffsäure auf Natriumchlorat gewonnen. Da Chlordioxid bei höheren Temperaturen ausserordentlich explosiv ist, arbeitet man bei verhältnismässig niedriger Temperatur und mit hintereinanderliegenden Überlaufgefässen oder in einer Reaktionskolonne. Hierbei lässt man durch eine Reihe von hintereinandergeschalteten und in der Höhe gestaffelten Reaktionsgefässen, die z. B. als Kolonne angeordnet sind, Chlorat- und Salzsäurelösungen hindurchfliessen. In entgegengesetzter Richtung drückt oder saugt man einen Strom von inertem Gas hindurch, z. B. Luft oder Stickstoff, um das in den einzelnen Reaktionsräumen entstehende Chlordioxid auszuspülen und dabei auf ungefährliche Konzentrationen zu verdünnen. Das Gas durchströmt die Flüssigkeit mittels bis auf den Boden der Reaktionsräume reichender Gasleitungsrohre bzw. Gastauchungen.Chlorine dioxide is increasingly being obtained through the action of hydrochloric acid on sodium chlorate. Since chlorine dioxide is extremely explosive at higher temperatures, the process is carried out at a relatively low temperature and with overflow vessels one behind the other or in a reaction column. Here you can through a series of cascaded and staggered in height reaction vessels, the z. B. are arranged as a column, chlorate and hydrochloric acid solutions flow through. In the opposite direction, one presses or sucks a stream of inert gas, e.g. B. air or nitrogen to rinse out the chlorine dioxide formed in the individual reaction rooms and thereby dilute to harmless concentrations. The gas flows through the liquid by means of gas line pipes or gas immersions reaching to the bottom of the reaction spaces.
Bei der genannten Erzeugung von Chlordioxid aus Natriumchlorat und Chlorwasserstoffsäure laufen im wesentlichen zwei Reaktionen gemäss folgenden Reaktionsgleichungen ab:
Die zweite Reaktion ergibt kein Chlordioxid. Diese Reaktion muss daher soweit wie möglich unterdrückt werden. Eine Voraussetzung dafür ist ein möglichst geringer HCI-Überschuss in der Reaktionsflüssigkeit. Dies wiederum bedingt lange Verweilzeiten, insbesondere dann, wenn die teilweise verbrauchte Elektrolytlösung in eine Chloratelektrolyse rezirkuliert wird, wie im sogenannten Kesting- oder im München-Verfahren. In diesem Falle würde restliche Chlorwasserstoffsäure in der Elektrolyse zu Wasserstoff und Chlor zersetzt werden. Beides sind jedoch unerwünschte Produkte in der Chloratelektrolyse. Um diese unerwünschten Produkte zu vermeiden, muss ein ClO2-Reaktor in mehrere Stufen bzw. Reaktionsräume unterteilt sein, z. B. in sechs, wie aus dem Kesting-Verfahren bekannt. In den obersten 4 Reaktionskammern wird bei von oben nach unten steigenden Temperaturen CI02 erzeugt. In den untersten beiden Kammern wird durch Temperatursteigerung bis zum Siedepunkt die restliche Chlorwasserstoffsäure mit dem noch vorhandenen NaCI03 unter Erzeugung von NaCI, CI2 und H20 umgesetzt. Wegen der hohen Temperaturen und der korrosiven Medien werden die Cl02-Reaktoren oft aus Titan gefertigt. Die oberen Stufen eines Reaktors laufen bei niedrigen Temperaturen, könnten daher auch aus anderen Materialien als Titan, z. B. aus Werkstoffen auf Basis von keramischem oder Kunststoff-Material, hergestellt werden. Da man aber mit der Möglichkeit einer CI02-Zersetzung mit entsprechenden Temperatur- und Drucksteigerungen rechnen muss, ist es zweckmässig, auch für die bei niedrigeren Temperaturen betriebenen oberen Reaktionsstufen Titan als Konstruktionswerkstoff zu verwenden.The second reaction gives no chlorine dioxide. This reaction must therefore be suppressed as much as possible. A prerequisite for this is a minimal HCI excess in the reaction liquid. This in turn requires long dwell times, especially when the partially used electrolyte solution is recirculated to chlorate electrolysis, as in the so-called Kesting or Munich process. In this case, residual hydrochloric acid would be decomposed to hydrogen and chlorine in the electrolysis. However, both are undesirable products in chlorate electrolysis. In order to avoid these undesired products, a ClO 2 reactor must be divided into several stages or reaction spaces, e.g. B. in six, as known from the Kesting process. In the top 4 reaction chambers, CI0 2 is generated at temperatures rising from top to bottom. In the bottom two chambers, the remaining hydrochloric acid is reacted with the NaCl0 3 still present to produce NaCl, CI 2 and H 2 0 by increasing the temperature to the boiling point. Because of the high temperatures and the corrosive media, the Cl0 2 reactors are often made of titanium. The upper stages of a reactor run at low temperatures and could therefore be made of materials other than titanium, e.g. B. made of materials based on ceramic or plastic material. However, since the possibility of a CI0 2 decomposition with corresponding temperature and pressure increases must be expected, it is expedient to use titanium as the construction material for the upper reaction stages operated at lower temperatures.
Um ein Zersetzen des Chlordioxids zu vermeiden, muss man das CI02 auf einen Partialdruck von ca. 0,1 at reduzieren. Dies erfolgt durch Anwendung von vermindertem Druck oder durch Verdünnen mit Luft oder einer Kombination aus beiden. Die Konstruktion des Reaktors muss demzufolge für Vakuum und Druck ausgelegt werden, wobei der Unterdruck bei Luftverdünnung kleiner ist als bei der Anwendung von nur vermindertem Druck. Um nun das CI02 aus der Lösung zu strippen und um die Bildungsreaktion des Chlordioxids (Gleichung 1 ) nicht zu stoppen, muss man die Luft durch die Reaktionslösung perlen lassen oder sie hindurchsaugen. Den Widerstand der Reaktionsflüssigkeit kann man nun zum Aufbau eines Unterdrucks benutzen, wobei sich vorteilhafterweise das Vakuum mit steigender CI02-Konzentration erhöht.To avoid decomposition of the chlorine dioxide, the CI0 2 must be reduced to a partial pressure of approx. 0.1 at. This is done by applying reduced pressure or by dilution with air or a combination of both. The design of the reactor must therefore be designed for vacuum and pressure. In order to strip the CI0 2 from the solution and not to stop the formation reaction of the chlorine dioxide (equation 1), the air must be bubbled through or sucked through the reaction solution. The resistance of the reaction liquid can now be used to build up a negative pressure, the vacuum advantageously increasing with increasing CI0 2 concentration.
Demgegenüber muss bei Arbeitsweisen mit stark verminderten Drücken dieser Tatsache durch eine entsprechend ausgelegte Konstruktion der Reaktionskammern Rechnung getragen werden. Ersichtlich wird hierdurch der konstruktive und materielle Aufwand erhöht.In contrast, this must be taken into account in working methods with greatly reduced pressures by a correspondingly designed construction of the reaction chambers. This clearly increases the constructive and material effort.
Der Erfindung liegt die Aufgabe zugrunde, diese Nachteile zu beseitigen. Zur Lösung dieser Aufgabe geht die Erfindung aus von einem Reaktor für die Herstellung von Chlordioxid aus Natriumchlorat und Chlorwasserstoffsäure unter Einleitung eines Trägergas-Gegenstromes, wobei der Reaktor mehrere senkrecht übereinander angeordnete, durch Gastauchungen bzw. Gaseinleitungen und durch abgetauchte Flüssigkeitsüberläufe miteinander verbundene Reaktionsräume aufweist.The object of the invention is to eliminate these disadvantages. To achieve this object, the invention is based on a reactor for the production of chlorine dioxide from sodium chlorate and hydrochloric acid with the introduction of a carrier gas countercurrent, the reactor having a plurality of reaction spaces which are arranged vertically one above the other and are connected to one another by gas immersion or gas introduction and by submerged liquid overflows.
Bei einem Reaktor der genannten Art ist die Erfindung gekennzeichnet durch
- a) zur Reaktormitte hin kegelmantelförmig ansteigenden Boden des jeweiligen Reaktionsraumes mit
- b) über der Kegelmantelfläche angeordneter, kegelförmiger Gastauchung, wobei
- c) die Austrittsstelle der Gastauchung auf der Kegelmantelfläche mit der Massgabe angeordnet ist, dass die Reaktionsflüssigkeit innerhalb (V 1) und ausserhalb (V 2) des Gastauchungsringes praktisch das gleiche Volumen aufweist.
- a) towards the center of the reactor with the cone-shaped rising bottom of the respective reaction space
- b) conical gas immersion arranged above the surface of the cone, wherein
- c) the exit point of the gas immersion is arranged on the surface of the cone with the proviso that the reaction liquid inside (V 1) and outside (V 2) of the gas immersion ring has practically the same volume.
Die Figur der Zeichnung zeigt in schematischer Darstellung einen Längsschnitt durch einen Reaktor gemäss der Erfindung. Am Kopf der Kolonne wird über Leitung 1 eine wässerige Lösung von Natriumchlorat und Chlorwasserstoff in den Reaktor 8 eingeführt und über Leitung 6 wird die verbrauchte Reaktionslösung ausgeschleust. Ein Trägergasstrom aus inertem Gas wird über Leitung 2 im Gegenstrom eingeführt. Mit 3 ist der kegelmantelförmig ansteigende Boden der Reaktionskammer bezeichnet und mit 4 die über dem Boden 3 angeordnete kegelmantelförmig bzw. trichterförmig ausgebildete Gastauchung 4. Durch die Rohre 5 erfolgt der Überlauf der Reaktionsflüssigkeit aus der jeweils darüberliegenden Reaktionskammer. V 1 und V 2 sind die praktisch gleichen Flüssigkeitsvolumina der einzelnen Reaktionskammern mit den jeweiligen Berührungspunkten oder Linien S. Die über der Gasaustrittsstelle der Tauchung 4 liegende Flüssigkeitssäule ist mit FI bezeichnet.The figure of the drawing shows a schematic representation of a longitudinal section through a reactor according to the invention. At the top of the column, an aqueous solution of sodium chlorate and hydrogen chloride is introduced into the
Mit der besonderen Ausgestaltung der Reaktionskammern gemäss der Erfindung wird erreicht, dass das Volumen der Reaktionsflüssigkeit innerhalb des Einleitungsringes (V 1 ) und ausserhalb des Einleitungsringes (V 2) praktisch gleich ist und mithin die Volumina auch praktisch gleiches Gewicht aufweisen. Infolge dieser Aufteilung in praktisch gleiche Volumina (V 1 und V 2) liegt die Austrittsstelle des Gasstromes aus Trägergas wie Luft und Reaktionsgas, wie Chlordioxid und Chlor, in den einzelnen Reaktionskammern jeweils sozusagen am Schnittpunkt S der beiden Volumina (s. Figur) und damit genau unterhalb der jeweiligen Flüssigkeitssäule (Fl). Da somit der Druck des Gases genau dem Gewicht der darüberliegenden Flüssigkeitssäule entspricht und das Gas ferner hindurchgesaugt wird, so ist der Reaktor während des Betriebes entlastet. Das heisst, nur im Stillstand sind die jeweiligen Reaktionsböden mit dem Gewicht der Reaktionsflüssigkeit belastet, hingegen im Betriebszustand voll entlastet, da der Flüssigkeitsdruck genau dem angelegten Unterdruck entspricht. Die kegelmantelförmige Gastauchung besitzt keinerlei Öffnungen im Kegelmantel, durch die Reaktionsgase einseitig entweichen könnten. Somit wird ein Ringspalt, der durch senkrecht stehende Stege unterbrochen sein kann, als gleichmässige Gasaustrittsstelle geschaffen, der für die sichere und vorteilhafte Wirkungsweise des erfindungsgemässen Reaktors entscheidende Bedeutung besitzt.With the special design of the reaction chambers according to the invention it is achieved that the volume of the reaction liquid inside the inlet ring (V 1) and outside the inlet ring (V 2) is practically the same and, consequently, the volumes also have practically the same weight. As a result of this division into practically equal volumes (V 1 and V 2), the point of exit of the gas flow from carrier gas such as air and reaction gas, such as chlorine dioxide and chlorine, lies in the individual reaction chambers, so to speak, at the intersection S of the two volumes (see figure) and thus exactly below the respective liquid column (Fl). Since the pressure of the gas thus corresponds exactly to the weight of the liquid column above it and the gas is also sucked through, the reactor is relieved during operation. This means that the respective reaction trays are only loaded with the weight of the reaction liquid when it is at a standstill, but fully relieved in the operating state, since the liquid pressure corresponds exactly to the negative pressure applied. The cone-shaped gas immersion has no openings in the cone jacket through which reaction gases could escape on one side. Thus, an annular gap, which can be interrupted by vertical webs, is created as a uniform gas outlet, which is of crucial importance for the safe and advantageous mode of operation of the reactor according to the invention.
Der Vorteil des erfindungsgemässen Reaktors liegt in der besonders günstigen kompakten Bauform mit ökonomisch günstigen, geringen Blechstärken der Reaktionsböden aus hochwertigem Werkstoff, wie Titan, sowie in kurzen Leitungen und geringem Raumbedarf.The advantage of the reactor according to the invention lies in the particularly favorable compact design with economically favorable, low sheet thicknesses of the reaction trays made of high-quality material such as titanium, as well as in short lines and small space requirements.
Claims (1)
- A reactor for producing chlorine dioxide from sodium chlorate and hydrochloric acid, wherein an opposing stream of an entraining gas is introduced and which comprises a plurality of vertically superimposed reaction chambers, which are interconnected by immersed gas-feeding caps or gas inlets and by immersed downcomers for the liquid, characterized in thata) the bottom of each reaction chamber is conical and rises toward the center of the reactor,b) an immersed conical gas-feeding cap is disposed over the conical bottom, andc) the outlet of the immersed gas-feeding cap is disposed on the conical bottom in such a manner that the reaction liquid has virtually the same volume within (V 1 ) and outside (V 2) the annular rim of the immersed gas-feeding cap.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83200595T ATE13753T1 (en) | 1982-05-18 | 1983-04-26 | REACTOR FOR THE PRODUCTION OF CHLORINE DIOXIDE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3218649A DE3218649A1 (en) | 1982-05-18 | 1982-05-18 | REACTOR FOR THE PRODUCTION OF CHLORDIOXIDE |
| DE3218649 | 1982-05-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0095199A1 EP0095199A1 (en) | 1983-11-30 |
| EP0095199B1 true EP0095199B1 (en) | 1985-06-12 |
Family
ID=6163902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83200595A Expired EP0095199B1 (en) | 1982-05-18 | 1983-04-26 | Reactor for preparing chlorine dioxide |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0095199B1 (en) |
| AT (1) | ATE13753T1 (en) |
| BR (1) | BR8302603A (en) |
| DE (2) | DE3218649A1 (en) |
| FI (1) | FI72706C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3546010A1 (en) * | 1985-12-24 | 1987-06-25 | Karl Lohrberg | REACTOR FOR THE PRODUCTION OF CHLORDIOXIDE |
| DE3719878A1 (en) * | 1987-06-13 | 1988-12-29 | Metallgesellschaft Ag | REACTOR FOR GENERATING CHLORINE DIOXIDE FROM ALKALICHLORATE AND ACID |
| DE3819763A1 (en) * | 1988-06-10 | 1989-12-21 | Metallgesellschaft Ag | METHOD AND REACTOR FOR PRODUCING CHLORINE DIOXIDE AND CHLORINE FROM ALKALICHLORATE |
| DE3928747A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | METHOD FOR DISINFECTING HARD SURFACES WITH CHLORDIOXIDE |
| CN1062715C (en) * | 1998-04-30 | 2001-03-07 | 北京四价环境工程有限责任公司 | Method for preparing chlorine dioxide and its generation equipment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH366519A (en) * | 1961-10-06 | 1963-01-15 | Lonza Ag | Device for slow chemical reactions and for separating the reaction products |
| NL6906359A (en) * | 1969-01-29 | 1970-07-31 | Continuous preparation of chlorine dioxide | |
| JPS596915B2 (en) * | 1980-05-13 | 1984-02-15 | 日本カ−リツト株式会社 | Electrolytic production method of chlorine dioxide |
-
1982
- 1982-05-18 DE DE3218649A patent/DE3218649A1/en not_active Withdrawn
-
1983
- 1983-04-26 DE DE8383200595T patent/DE3360260D1/en not_active Expired
- 1983-04-26 AT AT83200595T patent/ATE13753T1/en not_active IP Right Cessation
- 1983-04-26 EP EP83200595A patent/EP0095199B1/en not_active Expired
- 1983-05-06 FI FI831564A patent/FI72706C/en not_active IP Right Cessation
- 1983-05-17 BR BR8302603A patent/BR8302603A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI72706C (en) | 1987-07-10 |
| DE3360260D1 (en) | 1985-07-18 |
| FI831564L (en) | 1983-11-19 |
| FI72706B (en) | 1987-03-31 |
| FI831564A0 (en) | 1983-05-06 |
| BR8302603A (en) | 1984-01-17 |
| ATE13753T1 (en) | 1985-06-15 |
| DE3218649A1 (en) | 1983-11-24 |
| EP0095199A1 (en) | 1983-11-30 |
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